Manufacture of divinyl-benzene compounds from corresponding ethylated benzene compounds



Patented Sept. 25, 1945 UNITED STATES PATENT -OFFlCE" MANUFAUIUBE F DIVINYL- POUNDS FROM OOBBES 'mmzsmt oomrounmc nurt- ATED BWZENE COMPOUNDS Robert'B. Drelsbach. Midland, Klein, assign! to Hie Dow (Jhemlcal Company, Midland, Mich a corporation of Michigan No Drawing. Application September 10, 1941,

' Serial No. 410,264

This invention concerns an improved method for the manufacture of divinyl-benzene compounds having the general formula:

wherein X is hydrogen, or a halogen, e. g. chlorine or bromine, or a methyl or ethyl group, by the pyrolytic dehydrogenation of corresponding ethylated compounds. It particularly concerns the productionof divinyl-benzene Iromdiethyl benzene and/ or ethyl-vinyl-benune;

Divinyl-benzene is known to polymerizevery which is insoluble in benzene and other usual organic solvents. It is also known that the addi-, tion of a small proportion of divinyl-benzene to styrene followed by polymerization results in for: mation of a clear glass-like resin whichis insoluble in solvents capable of dissolving polysty-'.

rene alone. Because of such properties, there are n numerous uses to which divinyi-benzene wouldbe adapted, provided that it could be manufactured at reasonable cost. i

Of the several methods heretofore employedin' Although it should theoretically be possible to form divinyl-benzene from the less expensive and more readily available starting material, diethylbenzene, by dehydrogenating the latter in accordance with the equation:

nio=cn cn=cm+m no method for successfully eflecting this reaction has heretofore known. To the contrary, it is repeatedly taughtin the art that the principal vinyl aromatic compound obtainable by the pyrolytic dehydrogenation of diethyl-benzene is ethyl-vinyl -benzene, little if any divinyll benzene bein formed. readily with formation of a transparent resin 8 My researches have confirmed this teaching, 1. e. I have found that when diethyl-benzene is pyrolyzed'by usual methods, ethyl-vinyl-benzene is formed as the principal vinyl aromatic product,

together in somehinstances' with very small amounts of styrene and/or divinyl benzene' Not only was the'yield of divinyl benzene almost negligible', but separation by distillation of the small amounts ofdivirwl-benzene sometimes formed is as diilicult and impractical. 11-. is moredimcult to separate divinyl-benzene by distillation from a pyrolysis mixture containing only a small concentration, e. g. less than 10 per cent by weight, of the same than from ;mixtures containing the 80 compound in higher concentrations, since the prolonged heating required to "fraetionate divinyl-benzene from a mixture of low concentration usually causes polymerization I Attempts to produce divinyl benzene in higher yield by pyrolyzing" diethyl-benzene'under more vigorous conditions, e. g, by raising the temperature or extending the time of reaction, failed and merely increased the amount of by-product formation. From these experiments, it appeared 40 that the usual ethyl-vinyl-benzene' product is too unstable to permit pyroiyti'c dehydrogenation of the s v e to form divinyl-benzene without excessive by -product formation. However, another possible explanation for the failure to obtain divinyl benzene in substantial yield by the pyrolysis of methyl-benzene wouldbe that one or more of 1 the products other thanethyl-vinyl-benzen epg. hydrogen, unreacted "diethyl-be'nzene, ethyl benzene, or benreneyetc which in present in t0 the reacting mixture together with thefethyl and vinyl-benzene durixm its formation, might prevent further dehydrogenation of the ethyl-vinyl-ben- I first pyrolyzing the latter as usuaito obtain ethyl-vinyl-benzene as the major vinyl aromatic product, concentrating the ethyl-=vinyl benzene together if desired with any divinyl-benzene present, and pyrolyzing the concentrated material. In the second of these pyrolysis steps, divinylbenzene is formed in good yield and in a concentration suiilciently high to permit separation of the same from the reaction mixture by distillation. 1

The above-mentioned pyrolysis reactions may each be carried out at temperatures between 450 and 1000 C. employing any of the various pro-- cedures heretofore known for the pyrolysis of ethyl-benzene to form styrene. -The time 01' reaction, 1. e. the time over which the material ismaintained at a pyrolyzing temperature, should. of course, be restricted sufllciently so as to avoid appreciable carbonization. The employment of a very brief reaction period is particularly important when operating at temperatures above 700 C..

In practice, pyrolysis of the diethyl-benzene is preferably carried out by passing liquid or yaporized diethyl-benzene into admixture with asses this second pyrolysis are condensed by cooling.

The mixture so obtained contains divinyl-benzene as a major product, and the divinyl-benzene is present in high enough concentration'to permit its separation by distillation. The distillation is carried out under vacuum and preferably in the presence of a substance such as sulphur,

tertiary-=butyl-catechol, or pyrogallol, etc. which serves to inhibit polymerization of the divinylbenzene. Unreacted ethylr-vinyl-benzene or diethyl-benzene recovered in this distillation is recycled in the process for the production of additional divinyl-benz-ene,

ing its scope.

steam which has been superheated sumciently to provide the heat of pyrolysis. Usually steam heated to temperatures between 700 and 1200 C. is used in such proportion as to form with the diethyl-benzene a mixturehaving a temperature between 850 and 950 (land the mixture so i formed is cooled to below 650 C. within 1 second,

and preferably within 0.25 second, after its formation. However, by. operating at lower temperatures in the presence or absence of dehydrogenating catalysts or agents, such as sulphur, metal oxide catalysts, activated charcoal, etc..

- longer periods of reaction may be employed and immediate cooling. of the reacted mixture is not imperative.

The vapor mixture produced by the pyrolysis of diethyl-benzene is cooled sufllciently to liquefy the aromatic reaction products and separate them i from the gaseous mixture of hydrogen and lower aliphatic hydrocarbons, e. g. ethane, methane. ethylene, etc., also formed in the pyrolysis. The liquid condensate is fractionally distilled, preferably under vacuum and in the presence of a polymerization inhibitor such as sulphur or a polyhydrlc phenol, to obtain a fraction rich in ethyl-vinyl-benzene and which may also contain divinyl-benzene, if formed. This fractional distillation is carried out with suillcient care so that the concentration of dehydrogenated diethylbenzene," i. e. of ethyl-viny -benzene plus divinyl-benzene, in the fraction thus collected is at least 75 per cent my weight and preferably per cent or more. 4

The concentrated ethyl-vinyl-benzen which may contain minor amounts of divinyl-benzene and/or unreacted diethyl-benzene, etc., is pyrolyzed under conditions similar to those hereinbefore described for the initial pyrolysis of the diethyl-benzene, and the aromatic products of monovinyl aromatic compound .trated, and is then itself pyrolyzed unreacted diethyl-benz'ene,

Example methyl-benzene was vaporized and passed in being such as to form a mixture having a temperatureof 700 C. The mixture thus formed was passed immediately through a bed of activated charcoal at such rate that thecontact time, i. e. the time required for an integral portion of the mixture to traverse the bed, was only 0.025 second. The mixture was then cooled to condense thearomatic products and thus separate them from the hydrogen and other permanently gaseous reaction products; The condensate was analyzed and found to contain less than 1 per cent by weight of benzene, 3 per cent oi styrene, 3.5 per cent of divinyl-benzene, 36 per cent of and 18.4 per cent of ethyl-vinyl-benzene. It was fractionally distilled under vacuum to obtain. a fraction consisting largely of the ethyl-vinyl-benzene. This fraction was pyrolyzed at a temperature of 725 C. under conditions otherwise similar to those employed in pyrolyzing the diethyl-benzene. The reaction mixture was cooled to oondense'the aromatic products. The condensate was found to contain approximately 2.8 per cent by weight of ethyl benzene, 8.4 per cent of methyl-benzene, 6.7 per production of divinyl-benzene from diethyl-benzene, but may also be applied in producin nuclear substituted divinyl-benzenes wherein the nuclear substituents are halogen or methyl or ethyl groups. For instance, it may be applied in making divinyl-ethyl-benzene from triethyl-benzene, in making divinyl-to'luene from diethyltoluene, in making divinyl-chlorobenzene from diethyl-chlorobenzene, in making divinyl-bromobenzene from diethyl-bromobenzene, in making divinyl-dichlorobenzene from diethyl-dichlorobenzene, etc. In all such instances, the starting compoun is pyrolyzed to-obtain a corresponding to obtain the desired divinyl aromatic product.

Other modes of pplying the principle of the invention may be employed instead of those ex- F m nse method herein disclosed, provided the stepor ns stated by any of the following claim or the equivalent of such stated step or steps be employed.

1 therefore particularly point out and distinctly claim as my invention:-

which is concenbeing made. as regards the bonization whereby it is further dehydrogenated to form divinyl-benzene.

2. In a. method for making a divinyl-benzene compound wherein a diethyl-benzene compoundhaving the general formula,

f 4:11.013. Q-cmom where X is a substituent selected from the group consisting of hydrogen, halogens, methyl and ethyl substitucnts, and n is an integer not exceeding 4, is pyrolyzed to form a corresponding ethyl-vinyl-benzene compound and the pyrolysis mixture is cooled to obtain a condensate comprising the ethyl-vinyl-benzene compound diluted with other aromaticcomponents oi the mixture, the steps of fractionally distilling the condensate to obtain a fraction thereof containing at least '75 per cent by weight of the ethylvinyl-benzene compound, passing this fraction through a reaction zone at a rate of flow sufiicient to prevent substantial carbonization while heating the mixture within said zone to a reaction temperature between 450 and 1006" 0., and promptly cooling the reaction mixture as it flows from said zone.

3. In a method for makin a divinyl-henzene compound wherein a methyl-benzene compound having the general formula,

where X is a suhstituent selected from the group consisting of hydrogen, halogens, methyland ethyl substituents, and n is an integer not exceeding 4. is pyrolyzed to form a corresponding ethyl-vinyl-benzene compound and the pyrolysis mixture is cooled to obtain a condensate comprising the ethyl-vinyl-benzene compound dilutecl with other aromatic components of the mixture, the steps of iractionally distilling the condensate to obtain a fraction containing at Beast '15 per cent by weight of the ethyl-vinyl-benzene compound, vaporizing this fraction and passing the vapors into admixture with steam which is superheated to a temperature above 700 C. to form a pyrolysis mixture havin a temperature between 650 and 950 (2., and promptly thereafter cooling the 4. In a method for making divinyl-benzene wherein diethyl-benzene-"is pyrolyzed to form ethyl-vinyl-henzene and the pyrolysis mixture is cooled to obtain a condensate comprising the ethyl-l-benzene diluted with other aromatic components of the mixture, the steps 0! tractionaily distilling the condensate to obtain a fraction containing at least '15 per cent by weight of ethyl-vinyl-benzene, vaporizing this fraction and passing the vapors through a reaction zone at a rate oi flow sumcient to prevent substantial carbonization while heating the vapors within said zone to a reaction temperature between 650 and 950 0., and promptly cooling the reaction mixture as it flows irom said zone.

5. In a" method oi. ma divinyl-benzene wherein diethyl-henzene is pyrolyzed to form ethyl-vihyl-benzenc and the pyrolysis mixture is cooled to obtain a condensate comprising the ethyl-vinylbenzene diluted with other aromatic components of the mixture. the steps which consist in Emotionally distilling the condensate to obtain a fraction containing at least per cent by weight oi ethyl-vinyl-benzene, vaporizing this fraction and passing the vapors into admixture with steam which is superheated to a tempera, ture above 706 (3. to form a pyrolysis mixture having a temperature between 650 and 950 (3.,

and promptly thereafter-mowing themixture to a temperature below 650 0.

am? a. DREISBACH. 

